CN108586213A - A kind of waste-heat recovery device in ethene hydroformylation reaction process and its method - Google Patents
A kind of waste-heat recovery device in ethene hydroformylation reaction process and its method Download PDFInfo
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- CN108586213A CN108586213A CN201810562833.5A CN201810562833A CN108586213A CN 108586213 A CN108586213 A CN 108586213A CN 201810562833 A CN201810562833 A CN 201810562833A CN 108586213 A CN108586213 A CN 108586213A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type
- F25B15/02—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas
- F25B15/06—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas the refrigerant being water vapour evaporated from a salt solution, e.g. lithium bromide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
- Y02B30/62—Absorption based systems
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention discloses the waste-heat recovery devices in a kind of ethene hydroformylation reaction process; including reactor; further include drum and refrigeration unit; the shifting thermal medium outlet of the reactor is connect with the shifting thermal medium gas phase import of the drum; the shifting thermal medium gaseous phase outlet of the drum is connect with the shifting thermal medium inlet of the refrigeration unit; the shifting thermal medium liquid-phase outlet of the drum is connected with the shifting thermal medium inlet of the reactor, and the shifting thermal medium outlet of the refrigeration unit is connected with the shifting thermal medium fluid inlet of the drum.The present invention also provides the methods of the waste heat in the recycling ethene hydroformylation reaction process for using the device.The present invention has the advantages that simple in structure, stable operation, operating cost be low, high-efficiency and economic.
Description
Technical field
The present invention relates to waste-heat recovery device and its methods, and in particular to remaining in a kind of ethene hydroformylation reaction process
Heat reclamation device and its method.
Background technology
Ethene hydroformylation reaction is the main method for preparing a variety of important organic solvents and industrial chemicals, such as positive propionic aldehyde
With normal propyl alcohol using ethene hydroformylation method as primary synthetic methods, ethene hydroformylation method also known as oxo synthesis are with second
Alkene, carbon monoxide, hydrogen are raw material, and the method for generation propionic aldehyde, this method are mainly characterized by product under the effect of the catalyst
Purity is high, and isomer-free generates, and separation is easy, is to produce the main method and developing direction of propionic aldehyde, and the production master of normal propyl alcohol
To include two parts：Positive propionic aldehyde reacts the subtractive process for making thick propyl alcohol and thick propyl alcohol with hydrogen, and raw material is positive propionic aldehyde and hydrogen
Gas.Carbonylation synthesis is strong exothermal reaction, and reaction heat is about 125kJ/mol, and the removal of heat is most important in reaction process.Second
Alkene hydroformylation reaction is divided into homogeneous catalyst technique and heterogeneous catalyst technique according to the difference of catalyst, such as Chinese patent public affairs
The number of opening CN105523891A, CN 105585437A, CN 104667976A, CN 102030622A, CN102336638A, the U.S.
Patent US4072709 etc..The heat that wherein homogeneous catalyst technological reaction releases takes reactor, reaction process out of by solvent
In the amount of heat that releases can not be utilized.Heterogeneous catalysis technological reaction temperature is low, and simultaneous reactions thermal discharge is especially big, causes
The ordinary shifting thermal medium of such as water, can not undergo phase transition in heat transfer process, and the shifting thermal efficiency is low, and reactor is easy temperature runaway；In addition,
The heat moved in thermal medium is difficult to effectively recycle, and recycling after typically exchanging heat with cooling water, this method causes
Heat waste, increases the operating cost of device.
Such as China Patent Publication No. CN107266289A, denomination of invention：A kind of dress using carbon dioxide production normal propyl alcohol
It sets and method.A kind of device and method using carbon dioxide production normal propyl alcohol of the disclosure of the invention, using carbon dioxide as raw material,
Including raw material mixed cell, buffer cell, reaction member, waste heat recovery unit, quenching unit, compression unit, separative element,
PSA unit, positive propionic aldehyde production unit and normal propyl alcohol production unit.The invention using carbon dioxide preparation ethylene, carbon monoxide,
Hydrogen and the raw material supply for producing its product as the positive propionic aldehyde in downstream, normal propyl alcohol；Make fuel using exhaust gas caused by technique
Issue additional steam.Shortcoming, which is the heat moved in thermal medium, to be recycled, and cause heat waste, increase the fortune of device
Row cost.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of simple in structure, stable operation, operating costs
Waste-heat recovery device in low, high-efficiency and economic ethene hydroformylation reaction process and its method.
To achieve the above object, the technical solution adopted by the present invention is：It is remaining in a kind of ethene hydroformylation reaction process
Heat reclamation device, including reactor go back drum and refrigeration unit, the shifting of the shifting thermal medium outlet and the drum of the reactor
Thermal medium gas phase import connects, and the drum moves shifting thermal medium inlet company of the thermal medium gaseous phase outlet with the refrigeration unit
It connects, the shifting thermal medium liquid-phase outlet of the drum is connected with the shifting thermal medium inlet of the reactor, the shifting of the refrigeration unit
Thermal medium outlet is connected with the shifting thermal medium fluid inlet of the drum.
Further：
As the preferred embodiment of the present invention, the reactor is provided at least one shifting thermal medium outlet.
As the preferred embodiment of the present invention, the reactor is preferably radial reactor.
As the preferred embodiment of the present invention, the reactor preferably axially reactor.
As the preferred embodiment of the present invention, the refrigeration unit is preferably lithium bromide absorption refrigerating set.
As the preferred embodiment of the present invention, the drum is provided at least one shifting thermal medium gas phase import.
The present invention also provides the methods of the waste heat in the recycling ethene hydroformylation reaction process for using the device, including with
Lower step：
(1) feed ethylene and synthesis gas enter reactor and are reacted, and the heat released in reaction process is entered instead
It answers the liquid phase of device to move thermal medium to absorb, liquid phase is moved during thermal medium absorption heat, and the shifting thermal medium of a part of liquid can phase transformation
At gaseous state, the shifting thermal medium of liquid phase is obtained；
(2) the shifting thermal medium for the liquid phase that step (1) obtains leaves point that reactor enters drum progress gas phase and liquid phase
From the shifting thermal medium of liquid phase reenters reactor and recycled, and gaseous shifting thermal medium is transported to refrigeration unit；
(3) gaseous state for entering refrigeration unit moves thermal medium by heat exchange, becomes liquid from gaseous state shifting thermal medium and moves thermal medium
Afterwards, it returns to drum and enters back into reactor and recycled.
As the preferred embodiment of the present invention, the shifting thermal medium preferably selects alkanes substance, more preferably isobutyl
One kind in alkane, normal butane, hexane, pentane and isopentane.
As the preferred embodiment of the present invention, the water as refrigerant initial temperature of the refrigeration unit is preferably 12-35 DEG C, stream
Amount is preferably 150-860 ton hours.
As the preferred embodiment of the present invention, the pressure of the drum is preferably controlled to 0.1-0.8Mpa, and temperature is preferred
Control is 60-160 DEG C.
The ethene hydroformylation reaction occurred in reactor is strong exothermal reaction, and reaction temperature is at 70-180 DEG C.It reacted
The amount of heat generated in journey is undergone phase transition by a part of alkanes shifting thermal medium heat being carried away to drum.
Drum receives the shifting thermal medium of reactor, is detached to the shifting thermal medium of gas phase and liquid phase, the shifting heat of liquid phase
Medium comes back to reactor, is saturated gaseous shifting thermal medium and is transported to refrigeration unit.
Refrigeration unit receives the gaseous state that drum comes and moves thermal medium, absorbs the heat that gaseous state moves thermal medium, and gaseous state is moved heat
Medium is cooled to after liquid moves thermal medium, is returned to drum and is entered back into reactor and is recycled.The refrigeration unit of the present invention is excellent
It is selected as lithium bromide absorption refrigerating set, lithium bromide absorption refrigerating set is using lithium-bromide solution as absorber material, with water
For refrigerant solution, using water, evaporation endothermic achievees the purpose that refrigeration in high vacuum.Water as refrigerant is generally 15-35 DEG C and enters bromine
Change lithium unit, be cooled to 7-15 DEG C be delivered to other cooling equipment used as low-temperature receiver.
Because ethene hydroformylation reaction response device temperature is relatively low, amount of heat can be released during simultaneous reactions, when
It will not be undergone phase transition as 100 DEG C or less when moving thermal medium using water when reaction temperature is relatively low, it can not be by a large amount of reaction heat band
Go out reactor, therefore, the device of the invention moves thermal medium using alkanes, moves thermal medium and selects alkanes (such as iso-butane, positive fourth
Alkane, hexane, pentane, isopentane etc.) can be in the relatively low medium undergone phase transition of reaction temperature, it can effectively will be big
The reaction heat of amount takes reactor out of.
Compared with prior art, the invention has the advantages that：
1, simple in structure, stable operation, reactor are provided at least one shifting thermal medium outlet, and drum is provided at least one
A shifting thermal medium gas phase import, can effectively remove the heat in reaction process；Moving thermal medium using alkanes can be anti-
It is undergone phase transition in the case of answering temperature relatively low, effectively takes a large amount of reaction heat out of reactor, so that reacting balance is carried out, reacted
Journey is without temperature runaway phenomenon.
The heat moved in thermal medium can be converted into cold water by 2, high-efficiency and economic by refrigeration unit, for it is follow-up other
The equipment for needing cold, improves the economy of device entirety, and cryogen coolant-temperature gage reduces by 8 DEG C or more.
Description of the drawings
Fig. 1 is the flow diagram of the waste-heat recovery device in the ethene hydroformylation reaction process of the present invention.
In figure, reactor 1, drum 2, refrigeration unit 3.
Specific implementation mode
As shown in Figure 1, the waste-heat recovery device in the ethene hydroformylation reaction process of the present invention, including reactor 1, also
Including drum 2 and refrigeration unit 3, the shifting thermal medium outlet of reactor 1 is connect with the shifting thermal medium gas phase import of drum 2, drum 2
Shifting thermal medium gaseous phase outlet connect with the shifting thermal medium inlet of refrigeration unit 3, the shifting thermal medium liquid-phase outlet of drum 2 with react
The shifting thermal medium inlet of device 1 is connected, and the shifting thermal medium outlet of refrigeration unit 3 is connected with the shifting thermal medium fluid inlet of drum 2.
Production procedure is (by taking the synthesis of propionic aldehyde as an example)：Feed ethylene and synthesis gas enter reactor 1 and carry out reaction generation
Propionic aldehyde and some other components, the liquid phase that the amount of heat released in reaction process is entered reactor 1 are moved thermal medium and are absorbed,
Liquid phase is moved during thermal medium absorption heat, and the shifting thermal medium of a part of liquid can mutually become gaseous state, and ratio is in 2-20%；Gas-liquid
The shifting thermal medium of phase leaves reactor 1 and enters drum 2, and the thermal medium that moves into the liquid phase of drum 2 carries out gas phase and liquid phase
Separation, the shifting thermal medium of liquid phase reenter reactor 1 and are recycled, and are saturated gaseous shifting thermal medium and are transported to refrigeration unit 3；
Gaseous state shifting thermal medium into refrigeration unit 3 is exchanged heat by refrigeration unit 3, after gaseous state becomes liquid shifting thermal medium, weight
New return drum 2 enters back into reactor 1 and is recycled.
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail, but the present invention and not only limits
In the embodiment described.
Embodiment 1
A kind of waste-heat recovery device in ethene hydroformylation reaction process, including reactor 1 (axial flow reactor, setting
There are one move thermal medium outlet), further include drum 2 (there are one move the import of thermal medium gas phase for setting) and 3 (lithium bromide of refrigeration unit
Absorption refrigeration unit), the shifting thermal medium outlet of reactor 1 is connect with the shifting thermal medium gas phase import of drum 2, the shifting of drum 2
Thermal medium gaseous phase outlet is connect with the shifting thermal medium inlet of refrigeration unit 3, shifting thermal medium liquid-phase outlet and the reactor 1 of drum 2
Shifting thermal medium inlet be connected, the shifting thermal medium outlet of refrigeration unit 3 is connected with the shifting thermal medium fluid inlet of drum 2.
The waste heat during propionic aldehyde is prepared using device recycling ethene hydroformylation reaction, state modulator is as follows：
Shifting thermal medium is normal butane；The temperature that the liquid phase of control into reactor 1 moves thermal medium is 70 DEG C, and pressure is
0.8Mpa, liquid phase are moved during thermal medium absorption heat, and the shifting thermal medium of a part of liquid can mutually become gaseous state, and ratio is 8%；
The pressure for controlling drum 2 is 0.8Mpa, and temperature is 70 DEG C；The water as refrigerant initial temperature for controlling refrigeration unit 3 is 20 DEG C, and flow is
450 ton hours.
As a result：Reacting balance carries out, and reactor 1 is without temperature runaway phenomenon in reaction process；The cryogen coolant-temperature gage of refrigeration unit 3 drops
To 10 DEG C.
Embodiment 2
A kind of waste-heat recovery device in ethene hydroformylation reaction process, including reactor 1 (radial reactor, setting
There are two move thermal medium outlet), further include drum 2 (there are two move the import of thermal medium gas phase for setting) and 3 (lithium bromide of refrigeration unit
Absorption refrigeration unit), the shifting thermal medium outlet of reactor 1 is connect with the shifting thermal medium gas phase import of drum 2, the shifting of drum 2
Thermal medium gaseous phase outlet is connect with the shifting thermal medium inlet of refrigeration unit 3, shifting thermal medium liquid-phase outlet and the reactor 1 of drum 2
Shifting thermal medium inlet be connected, the shifting thermal medium outlet of refrigeration unit 3 is connected with the shifting thermal medium fluid inlet of drum 2.
The waste heat during propionic aldehyde is prepared using device recycling ethene hydroformylation reaction, state modulator is as follows：
Shifting thermal medium is iso-butane；The temperature that the liquid phase of control into reactor 1 moves thermal medium is 60 DEG C, and pressure is
0.77Mpa, liquid phase are moved during thermal medium absorption heat, and the shifting thermal medium of a part of liquid can mutually become gaseous state, and ratio exists
7%；The pressure for controlling drum 2 is 0.77Mpa, and temperature is 60 DEG C；The water as refrigerant initial temperature for controlling refrigeration unit 3 is 20 DEG C,
Flow is 470 ton hours.
As a result：Reacting balance carries out, and reactor 1 is without temperature runaway phenomenon in reaction process；The cryogen coolant-temperature gage of refrigeration unit 3 drops
To 12 DEG C.
Embodiment 3
A kind of waste-heat recovery device in ethene hydroformylation reaction process, including reactor 1 (radial reactor, setting
There are three move thermal medium outlet), further include drum 2 (there are three move the import of thermal medium gas phase for setting) and 3 (lithium bromide of refrigeration unit
Absorption refrigeration unit), the shifting thermal medium outlet of reactor 1 is connect with the shifting thermal medium gas phase import of drum 2, the shifting of drum 2
Thermal medium gaseous phase outlet is connect with the shifting thermal medium inlet of refrigeration unit 3, shifting thermal medium liquid-phase outlet and the reactor 1 of drum 2
Shifting thermal medium inlet be connected, the shifting thermal medium outlet of refrigeration unit 3 is connected with the shifting thermal medium fluid inlet of drum 2.
The waste heat during propionic aldehyde is prepared using device recycling ethene hydroformylation reaction, state modulator is as follows：
Shifting thermal medium is hexane；The temperature that the liquid phase of control into reactor 1 moves thermal medium is 130 DEG C, and pressure is
0.5Mpa, liquid phase are moved during thermal medium absorption heat, and the shifting thermal medium of a part of liquid can mutually become gaseous state, and ratio is 3%；
The pressure for controlling drum 2 is 0.5Mpa, and temperature is 130 DEG C；The water as refrigerant initial temperature for controlling refrigeration unit 3 is 35 DEG C, flow
For 210 ton hours.
As a result：Reacting balance carries out, and reactor 1 is without temperature runaway phenomenon in reaction process；The cryogen coolant-temperature gage of refrigeration unit 3 drops
To 15 DEG C.
Embodiment 4
A kind of waste-heat recovery device in ethene hydroformylation reaction process, including reactor 1 (radial reactor, setting
There are four move thermal medium outlet), further include drum 2 (there are four move the import of thermal medium gas phase for setting) and 3 (lithium bromide of refrigeration unit
Absorption refrigeration unit), the shifting thermal medium outlet of reactor 1 is connect with the shifting thermal medium gas phase import of drum 2, the shifting of drum 2
Thermal medium gaseous phase outlet is connect with the shifting thermal medium inlet of refrigeration unit 3, shifting thermal medium liquid-phase outlet and the reactor 1 of drum 2
Shifting thermal medium inlet be connected, the shifting thermal medium outlet of refrigeration unit 3 is connected with the shifting thermal medium fluid inlet of drum 2.
The waste heat during propionic aldehyde is prepared using device recycling ethene hydroformylation reaction, state modulator is as follows：
Shifting thermal medium is isopentane；The temperature that the liquid phase of control into reactor 1 moves thermal medium is 90 DEG C, and pressure is
0.5Mpa, liquid phase are moved during thermal medium absorption heat, and the shifting thermal medium of a part of liquid can mutually become gaseous state, and ratio is 6%；
The pressure for controlling drum 2 is 0.5Mpa, and temperature is 90 DEG C；The water as refrigerant initial temperature for controlling refrigeration unit 3 is 15 DEG C, and flow is
540 ton hours.
As a result：Reacting balance carries out, and reactor is without temperature runaway phenomenon in reaction process；The cryogen coolant-temperature gage of refrigeration unit 3 drops
To 7 DEG C.
Claims (10)
1. the waste-heat recovery device in a kind of ethene hydroformylation reaction process, including reactor, which is characterized in that further include vapour
Packet and refrigeration unit, the shifting thermal medium outlet of the reactor are connect with the shifting thermal medium gas phase import of the drum, the vapour
The shifting thermal medium gaseous phase outlet of packet is connect with the shifting thermal medium inlet of the refrigeration unit, and the shifting thermal medium liquid phase of the drum goes out
Mouth is connected with the shifting thermal medium inlet of the reactor, and the shifting thermal medium outlet of the refrigeration unit is situated between with the shifting heat of the drum
Matter fluid inlet is connected.
2. the waste-heat recovery device in ethene hydroformylation reaction process according to claim 1, which is characterized in that described
Reactor is provided at least one shifting thermal medium outlet.
3. the waste-heat recovery device in ethene hydroformylation reaction process according to claim 1, which is characterized in that described
Reactor is radial reactor.
4. the waste-heat recovery device in ethene hydroformylation reaction process according to claim 1, which is characterized in that described
Reactor is axial flow reactor.
5. the waste-heat recovery device in ethene hydroformylation reaction process according to claim 1, which is characterized in that described
Refrigeration unit is lithium bromide absorption refrigerating set.
6. the waste-heat recovery device in ethene hydroformylation reaction process according to claim 1, which is characterized in that described
Drum is provided at least one shifting thermal medium gas phase import.
7. a kind of method of the waste heat in recycling ethene hydroformylation reaction process using device as described in claim 1,
It is characterized in that, includes the following steps：
(1) feed ethylene and synthesis gas enter reactor and are reacted, and the heat released in reaction process is entered reactor
Liquid phase move thermal medium absorb, liquid phase move thermal medium absorb heat during, the shifting thermal medium of a part of liquid can mutually become gas
State obtains the shifting thermal medium of liquid phase；
(2) the shifting thermal medium for the liquid phase that step (1) obtains leaves the separation that reactor enters drum progress gas phase and liquid phase, liquid
The shifting thermal medium of phase reenters reactor and is recycled, and gaseous shifting thermal medium is transported to refrigeration unit；
(3) thermal medium is moved by heat exchange, after gaseous state shifting thermal medium becomes liquid shifting thermal medium, weight into the gaseous state of refrigeration unit
New return drum enters back into reactor and is recycled.
8. the method for the waste heat in recycling ethene hydroformylation reaction process according to claim 7, which is characterized in that institute
It is one kind in iso-butane, normal butane, hexane, pentane and isopentane to state and move thermal medium.
9. the method for the waste heat in recycling ethene hydroformylation reaction process according to claim 7, which is characterized in that institute
The water as refrigerant initial temperature for stating refrigeration unit is 12-35 DEG C, and flow is 150-860 ton hours.
10. the method for the waste heat in recycling ethene hydroformylation reaction process according to claim 7, which is characterized in that
The pressure control of the drum is 0.1-0.8Mpa, and temperature control is 60-160 DEG C.
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| CN201810562833.5A CN108586213A (en) | 2018-06-04 | 2018-06-04 | A kind of waste-heat recovery device in ethene hydroformylation reaction process and its method |
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| CN201810562833.5A CN108586213A (en) | 2018-06-04 | 2018-06-04 | A kind of waste-heat recovery device in ethene hydroformylation reaction process and its method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970525A (en) * | 2019-04-23 | 2019-07-05 | 宁波巨化新材料有限公司 | A kind of hydroformylation device |
| CN111099976A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Refrigeration cycle system and method for preparing carbon pentaldehyde by hydroformylation of mixed carbon tetraolefin |
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| CN208545336U (en) * | 2018-06-04 | 2019-02-26 | 宁波巨化化工科技有限公司 | A kind of waste-heat recovery device in ethene hydroformylation reaction process |
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| CN104974026A (en) * | 2014-04-14 | 2015-10-14 | 中国石油化工股份有限公司 | Heat pump circulation system and heat pump circulation method used in hydroformylation process of low-carbon olefin |
| CN104098441A (en) * | 2014-06-05 | 2014-10-15 | 上海戊正工程技术有限公司 | Technology and device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gases and producing ethylene glycol through dimethyl oxalate hydrogenation |
| CN107266289A (en) * | 2017-05-22 | 2017-10-20 | 南京百润化工有限公司 | A kind of apparatus and method of utilization carbon dioxide production normal propyl alcohol |
| CN208545336U (en) * | 2018-06-04 | 2019-02-26 | 宁波巨化化工科技有限公司 | A kind of waste-heat recovery device in ethene hydroformylation reaction process |
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| CN111099976A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Refrigeration cycle system and method for preparing carbon pentaldehyde by hydroformylation of mixed carbon tetraolefin |
| CN109970525A (en) * | 2019-04-23 | 2019-07-05 | 宁波巨化新材料有限公司 | A kind of hydroformylation device |
| CN109970525B (en) * | 2019-04-23 | 2022-04-08 | 宁波巨化化工科技有限公司 | Hydroformylation device |
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